How to Unlock the Secret Characters
Jigglypuff is the easiest to unlock. To unlock Jigglypuff, you must complete the Classic Mode or Adventure Mode once, or play 50 Versus Mode matches.
To unlock Dr. Mario, you must beat the Classic Mode or Adventure Mode using Mario. Dr. Mario is very similar to Mario, but throws capsules instead of fireballs and wields a white sheet instead of a gold cape, or play 100 Versus Mode matches.
To unlock Pichu, Pikachu's evolutionary predecessor, you must clear Event Match #37 or play 200 Versus Mode matches. His B-button attack causes self-damage by one point.
To unlock Falco, you must beat the 100-Man Melee, or play 300 Versus Mode matches. Falco's blasters are not as rapid as Fox's. However, Falco's blasters pushes enemies from their tracks, compared to Fox's blasters.
To unlock Marth, you must use the initial (non-secret) characters in Versus mode at least once, or play 400 Versus Mode matches.
To unlock Young Link, or Child Link in Japan, you must complete Classic Mode ten times, or play 500 Versus Mode matches. Young Link is faster but weaker than adult Link. He shoots fire arrows, but his grab maneuver is shorter than adult Link's grab maneuver. Young Link's Kokiri Sword and bombs inflict less damage than adult Link's Master Sword and bombs. He can do wall jumps.
To unlock Ganondorf, the great evil that cursed Hyrule, you must complete Event Match #29, or play 600 Versus Mode matches. Ganondorf appears to be a replica of Captain Falcon
To unlock Mewtwo, you must play 700 Versus Mode matches or 20 total hours of Versus Mode.
To unlock Luigi, you must finish the first level of Adventure Mode with the seconds ones digit being a "2", e.g. 1:32:87. You will see Luigi stomp Mario making him fall down into the sea. After that you must finish the Adventure Mode in order to fulfill the goal, then Luigi is unlocked. Another way is to play 800 Versus Mode matches. Unlike Mario, Luigi's cyclone and uppercut attacks hit once per attack, and his fireballs defy gravity. His Green Missile move is similar to Pikachu's Skull Bash move.
To unlock Roy, you must complete Classic or Adventure Mode using Marth without using continues (or Smash tokens), or play 900 Versus Mode matches.
To unlock Mr. Game & Watch, you must complete Classic or Adventure Mode with the other characters, or complete the Target Test for all the other characters, or play 1000 Versus Mode matches.